Organic phosphates



Fatenieol Eco. i939 @RGANEC PHOSPHATES Edgar C. Britten and Clarence L. Moyle, Mid= land, lvlicli, assignors to The Dow Chemical Company, Midland, Michigan Mich, a corporation oi No Drawing. dipplicationiilugnst 2c, 1938, serial No. 225.9%

s claims. (or. zoo -rel 1o wherein R and 3 each represents an aromatic radical other than the 2,4-dibrompl1enyl radical. The new triaryl phosphates are useful as plas- .ticizing agents for cellulose derivative, e. a. cellulose acetate, nitrocellulose, ethyl cellulose-etc,

compositions. Many or" the new compounds are high-boiling, viscous liquids of high specific gravity. They do not. corrode or attack rubber or steel and, accordingly, are particularly valuable as core fluids for golf balls, wherein it is desirable which density of M0 to 1.85 and which does not attack. the rubber windings of the ball or corrode the steel needle used to inject the iiuid into the bell. 1

The new mixed phosphates having the above general formula may be prepared by reacting a phosphorus orryliallde, a. phosphorus osychlm ride or phosphorus oxybromide with 2,-dibromphenol to form a Zil-dibromphenyl phosphoric 3a acid dihalide and thereafter reacting such intermediate product with other phenols, e. g. phenol, cresol. naplithol, p-phenyl-phenol, etc. to form themixed trlaryl phosphateproduct. If desired, the order in which the different phenols are reacted may be changed. For example, a phosphorus oxyhalide may first be reacted with phenols other than Ze-dibrompbenol to form an aryl phosphoric acid mono-halide and the latter may then be reacted with 2,l-dibromphenol to form the desired mixed triaryl phosphate product. Also, the triaryl phosphate may be prepared by reacting 2,-l-dlbromphenol with any diaryl phosphoric acid monolnallde which does not contain the Zfi-dibromphenyl radical, e. phenyl naphthyl phosphoric acid chloride, dlxenyl phosphoric acid bromide, tertiarybutylphenyl cyclohexylphenyl phosphoric acid bromide, di-ter= tlaryoctylphenyl phosphoric acid chloride, etc.

Each of the above reactions is carried out by heating a mixture of the necessary reactants to a temperature at which hydrogen halide is readily evolved from the reaction mixture, preferably in the presence of a catalyst such as metallic calcium, magnesium or aluminum, or a chloride of magnesium, aluminum or iron. The reactions to employ a nigh-boiling, low-freezing liquid are preferably carried out at the lowest convenlent temperature, e. g. below about 200 0, since. at higher temperatures by-product formation may occur to an objectionable extent.

In preparing a mixed organic phosphate of 55, the present class from a phosphorus oxyhalide and the necessary phenolic compounds, the intermediate phosphoric acid halide product may be separated and purified, e. g. by fractional dis tillation, before carryingout the successive remy actions to form the mixed triaryl phosphate product. In practice, however, it is more convenient merely to distill unreacted phosphorus oxyhalide from the impure intermediate aryl phosphoric acid halide, add the necessary proportion of the second phenol and continue the reaction as hereinbefore described to obtain the final product. The latter consists largely of a single mixed triaryl phosphate having the general formula hereinbeiore presented, but may contain a minor proportion of a second mixed triaryl phosphate as well as some symmetrical triaryl phosphate formed by over-reaction of one of the phenol reactants with the phosphorus oxyhalide in the initial stage of the process. Such impure mixed phosphate product is adapted to most uses to which the pure compound is suitable and, accordingly, is a valuable product. When desired, the individual phosphates contained in such product can usually be separated by fractional U distillation.

The following examples will illustrate several ways in which the principle of the invention has been applied butshould not be construed as limiting the same:

- Example 1 A miirture of 504 grams (2.0 mols) of Z/l-dibromphenol, 924 grams (6.0 mols) of phosphorus oxychloride, and 2 grams of magnesium chloride was heated at a temperature of 90 to 95 C. for 2 hours, during which time hydrogen chloride was evolved from the mixture. When the reaction was complete, excess phosphorus oxychloride was distilled ofi under vacuum, 602 grams being recovered. The crude 2,4-dibromphenyl phosphoric acid dichloride was cooled to a temperature of approximately 70 C. and 376 grams (4.0 mols) of phenol were added. The temperstore was gradually raised to 156 C. over a period of'4 hours, at the end of which time the evolution of hydrogen chloride gas had ceased. The mixture was then cooled, washed with water to remove dissolved hydrogen chloride and fractionally distilled under vacuum. There was ob- 55 tained 779 grams of 2,4-dibromphenyl diphenyl phosphate, a slightly viscous liquid distilling at 273 to 283 C. ,under 8 millimeters pressure and a having a specific gravity of 1.627 at /25 C.

and an index of refraction,

'n=,=1.5992 2,4-dibromphenyl diphenyl phosphate has the formula B o r f, A Example 2 369 grams (1 mol) of 2,4-dibromphenyl phosphoric acid dichloride, prepared by reacting 2,4- dibromphenol with phosphorus oxychloride as in Example 1, was heated with 300 grams o t carvacrbl in the presence of 2 grams of magnesium chloride at a temperature of 95 to 165?;

C. for 4 hours. The reaction product was washed with water and fractionally distilled under vacuuma There was obtained 477 grams of '2,4-dibromphenyl di-carvacryl phosphate, a. pale yellow, viscous liquid distilling at 295 ,to 305 C.

, under 8 millimeters pressure and having a specific -2,4-dibromphenyl formula ,1

gravity of 1.400 at 25/25 C. and an index ofrefraction, I i n*,;=1.5s7a A dicarvacryl phosphate Ezramplefi I A mixture or 332 grams (0.9 mol) of 2,4411- brom-phenyl phosphoric acid dichl'oride,xprepared as in Example 1, grams (0.9 mol) of phenol, 93 grams (0.9 mol) of o-cresol, and 2 grams ofmagnesium chloride was heated for 6 hours at a temperature of to C. The

reaction product was washed and fractionally distilled under vacuum. ZA-dibromphenyl phenyl oecresyl phosphate was obtained as a pale yellow liquid distilling at 270 to 285 C. under 8,

millimeters pressure. It has a specific gravity of 1.564 at 25/25 0., an index of refraction,

' ri=1.5934 and the formula l om BQOP/ Example 4 2,4 dibromphenyl di--(0-cresy1) phosphate was prepared by reacting 2 mols of o-cresyl with 1 mol of crude 2,4-dibromphenylphosphoric acid chloride at 85 to C. for 4. hours as'in Example 2. Thereaction product was washed and fractioiially distilled whereby 2,4-dibromphenyl di-(o-cresyl) phosphate was obtained as a pale has the yellow, viscous liquid distilling at 290 to 300 C. under 6 millimeters pressure and having a specific gravity of 1.576at 25/25 (3., and an index of refraction,

. n==i.s9s9 and the formula other phenols, preferably hydrocarbon substituted phenols such as the alkyl, aryl, and cycloalkyl phenols, etc. For example, the 2,4-dibromophenyl phosphoric acid' dihalide may be reacted with p-ethylphenol to form 2,4-dibromphenyl di-(pethylphenyl) phosphate; with o-chlorphenol to form 2,4 -dibromphenyl di-(o-chlorphenyl) phosphate; with p-tertiarybutyiphenol and p-phenylphenol to form 2,4-dibromphenyl p-tertiarybutylphenyl p-xenyl phosphate; with 2,4-dimethylphenol to form 2,4-dibromphenyl di-2,4--dimethylphenyl) phosphate; with alpha naphthol to form 2,4-dibromphenyl di-(alpha-naphthyl) phosphate; with isopropyl phenol and m-cresol 'to form 2,4-dibromphenyl isopropylphenyl mcresyl phosphate; with 2,a,6,-triethyl phenol to form 2,4-dibromphenyl di-.(2,4,6-triethylphenyl) phosphate; with thymol and phenol to form 2,4-

dibromphenyl thymyl phenyl phosphateywith ocyclohexylphenol to form 2,4-dibromphenyl di- (o-cyclohexylphenyl) phosphate; etc.

'Other modesof applying the principle of our 1 invention may be employed instead of those explained, change being made as regards the inaterials employed, provided the products stated 'by any of the following claims or the equivalent of such stated products be obtained. 7

We therefore particularly point out and distinctly claim as our invention:

1. A mixed triaryl phosphate having the general formula wherein-R and R each represents an aromatic hydrocarbon radical.

2. A mixed triaryl phosphate having the general formula t O R I wherein each'R' represents the same hydrocarbon radical.

3. A mixed triarylphosphate having the general formula I 5 B o 1 (Y).,

wherein X and Y each represents a substituent aromatic selected from the class consistingot alkyl, aryl, specific gravity of ahout 1.400 at 25/25'C. and the and cycloalkyl radicals and hydrogen, and n represents an integer not greater than 3.

eral formula 4. A mixed triaryl phosphate having the genm- OP (mm wherein n represents an integer not greater Q Br- 0-! Br 6. 2,4-dibromphenyl di-carvacryl phosphate, a.

viscous liquid distilling at approximately 295 to 305 C. under 8 millimeters pressure and having a formula '7. 2,4-dibromphenyl phenyl o-cresyl phosphate, a pale yellow liquid distilling at approximately 270 to 285 C. under 8 millimeters pressure and having a specific gravity of about 1.564 at 25/25 C. and the formula OH: H (0 H 

